P-alkyl styrenes and their polymers



O Patented group is a primary normal alkyl group of at least six carbonatoms, including the higher alkyl derivatives such 2,802,812astetradecyl, hexadecyl, octadezyl, ego. The alkyl grclajup is notlimited to even numbere car on atom groups ut P'ALKYL STYRENES AND THEIRPOLYMERS 5 odd numbered carbon groups may also be prepared as Charles G.Overberger, Brooklyn, N. Y.,,-assignor;to L. A. will be illustrated. Aswill be pointed out below the para Dreyfus Company, Oak Tree, .N. J., acompany of n-alkyl styrenes up to dodecyl have a density ((14. of NewYork less thanabout 0.90.00 while beginning with ,the tetradecyl NoDrawing. Applicationjune261953 derivative they are solids having amelting point of not less than about 26 C. Senal 364473 The p-alkylstyrenes may be prepared by a .variety .of 13 Claimsestablishedprocedures. For example, benzene may .be

,acylated to give an -n-alkyl phenyl ketone and-the latter reduced to ann-alkyl benzene. The n-alkyl'benzene may This invention relates topolymers of alkyl styrenes, 15 then be acetylated by conventionalFriedel-Graftsproceand to intermediates for making the same including.alkyl dures to give p-acetyl-n-alkyl benzenes, and the ,latteracetophenones, alkylphenyl methyl carbinols, and alkyl reduced to pyphfinyl'methyl 'cafbinols which styrenes, particularly where the alkylgroup is'in the para then dehydraied'to desired py styfenes- SiflCeposition in any of the Stated compounds derivatiws, and many oftheintermed1ate compounds are novel, the folpolymers, and especially wherehigher alkyl fll) lowing tabulations are given of such novel compoundsresent in the -a1k 1 st renes and 01 mers made thereand their:properties' 5 p y y p y The p-alkylacetophenones, whose propertles aredebed in Table I were prepared by the method of Among the ob ects of thepresent lnventlon is the prosen duction of higher P styrenes and theirpolymers as Mowry, Renoll and Huber adapted from that of Perrler.

t t f th d f t An alkyl benzene is added to a pro-formed complex of W61as m erme es or 6 pro Ion 0 Sal s yrenes acetyl chloride and aluminumtrichloride dissolved in an and P ;iner;t:solve nt. Afterthereactionha-s eeased, the mixture S'fl further lfi a advantfigfis .Q-P -.i;s;neut-ral ized and extracted to remove the ,p-alkylracetoventionwill appear from. the more detailed descriptionset IP11311936, Afl th ttj l t h b gf v d,

forth below, it being understood that such more de- 39;the;crude;prodl1ct is purified by distillation or .r 1.

tailed description is 'given "by way of illustration and ex lizatiqn.

planation only, and not by way of limitation, since various.-References.-Mowry, Renoll and Hub,er,I. -Am. Chem.

changes therein may be-.-madef'by those--skilled in the art -.Soc,,'68,1105 (1946,), G. Perrier, Ben, 33, 815 (1900).

TABLE I p-Alkyl substituted acetophenones O" p R--- 0-011:

B. P., a Yield, R-group C./mm. M. P. Percent Formula Carbon HydrogenPercentage Composition Calcd. Found Oalcd. Found 4 I 83. 02 82. 97 10.84 11. 02 b 69. 7 CzoHazO 83. 27 83. 06 ll. 18 10. 91 0 75.0 0221130083. 48 83. 44 11. 46 11. 72 d 59. 3 024E400 83. 83. 51 11. 11. 61 B 61.7 CZGHMO 83. 83. 63 11. 90 11. 89

e Recrystallized fromimethanol.

b Yield reported 0115M.'P. 46.8-48.8 G. recrystallized from' absoluteethanol.

Yield reported on M. P. ;54.0 56.2 (3 recrystallized irorn ethyl ether.

Recrystallized from 1:2 ethylether-nrethanol.

6 'Yield reported on M. 1?. 58.6-64.29reerystallized from 1:1 ethylether-methanol.

without departing'from the scope and spirit of the present Table IIsummarizes the properties ofthe novel p-alkylinvention. phenyl methylcarbinols prepared from the corresponding In accordance with the presentinvention higher pp-alkyl acetophenqnes by r etifl m'with aluminumisoalkyl styrenes are synthesized and particularly utilized P PThe/method W S th described y A- L- in the preparation of polymersuseful for a variety of pur- Wilds.

poses. Such p-alkyl styrenes which are a part of this 7 Reference.-A. L.Wilds, :iQrganic Reactions, vol. invention, because of their utilizationin the production II, John Wiley and Sons, Inc., New York, N. Y., 1944,of polymers, are para alkyl styrenes in which the alkyl p. 203.

TABLE II p-Alkylphenylmethylcarbinols Percentage Composition B. P.,Yield, R-group O./mm. M. P Percent Formula Carbon Hydrogen Caled. FoundCalcd. Found 91. CraHzaO 81. 99 81. 78 11.18 11. 23

70. 3 C17H2s0 82. 82. 46 11.36 11.

78. 7 CzzHasO 82. 83. 28 12. 02 11. 87

n-O18H37- 93. 0 02611460 83. 35 83. 32 12. 38 12. 26

a 1th" 1.5030, d4 0.9282.

b Hydroxyl value, calcd. 193.5; found 189.7. Yield reported on M. P.48.050.0 reorganized, from ethanol.

6 Yield reported on M. P. 57.0-57.5", recrystallized from petroleumether (B. P. 28- 4 Yield reported on M. P. 62.8-63.3", recrystallizedfrom petroleum ether (B. P. 28-38). Yield reported on M. P. 67. 4-67. 9,recrystallized from petroleum ether.

The p-alkyl styrenes described in Table 111 were prepared by dehydrationof the corresponding p-alkyl-phenyl i the higher boiling styrenes,pressures of 1 to 2 mm. were used during dehydration. p-Alkyl C6, C8,C9, C10, C12, and

C14 styrenes were purified by sucessive distillation, p-Cie (B. P.28-36). Monomers were stored with inhibitor, usually p-tert-butylcatechol and purified by removing inhibitor with dilute sodium hydroxidefollowed by distillation or recrystallization before analysis andpolymerization.

Reference-C. G. Overberger and J. H. Saunders, Organic Reactions, JohnWiley and Sons, Inc., New

and C18 styrenes were recrystallized from petroleum ether 40 York, N.Y., 1948, vol. 28, p. 31.

TABLE III P- m q BOOB-on,

Percentage Composition Yield, R-group B. P., 0./mm. 12.." d Percent IFormula Carbon Hydrogen Oalcd. Found Oalcd. Found 89-90/1 1.5156 0.8742b 75.5 014E211 89.29 89.37 10.71 10.60 113-114/1 1. 5100 0.8714 b 78.4OmHn 88. 82 88.66 11.18 11. 51 -145/2. 3-2. 5 1. 5055 0. 8802 M1 51. 6(41. 2) 0 131 88. 62 88. 63 11.38 11. 47 139-14 1 1. 5045 0. 8706 b 85.5 OwHrs 88. 45 88. 32 11. 55 11. 68 158-163/1.21.4 1.5011 .8831 9 55.449.5 020 3: 88.16 87.79 11.84 11.88 192-196/2. 2 M. P. 26. 0-27. 0 I92.0 35. 6 CnHaa 87.92 87. 69 12. 08 12.00 M. P. 30. 831.4 8 32. 6 16. 30241140 87. 73 87.90 12. 27 12.41 M. P. 38.3-39.0 11 66.4 (63. 6) ONE87. 56 87. 32 12.44 12. 29

' Yield of Ca, Ca and C10 based on recovered carbinol; yield of On,

in parenthesis only based on monomer.

On, 014, C15 and or: based on monomer plus polymer; yield b Charge ofcarbinol 25 g., 1 g. fused KHSO4, 0.259 g. hydroqulnone, dropwiseprocedure, reaction temperatures -240 at 7 a Charge of carbiuol 22-15g., 1 g. fused KHSO4, 0.19 g. tert-butyl cetechol. Dodecylstyreneprepared by dropwise procedure, but C9, O14, 0m and 01g styrenesprepared by allowing portions of carbinol (2-3 ml.) to react at 25-50mm. and distilling by reducing the pressure to less than 5 mm.

d Main reaction temperature, 220-250. 9 220-250". 1 260-275".

. TABLE IV I Polymers of the p-dlkylstyrenes (EGO-IF) PercentageComposition Trans- 1 tion R-gronp [a T2131) Formula Carbon HydrogenOalcd. Found Calcd. "Found n-CzHa 2.02 27 G iding, 90.85 91.10 9.15-"9.02 n-O4Ho 1. 28 '6 OnHrt I 89.94 89.81 10.06 9.94 D-CBH13-- 1.57 27 0411 a, 89.29 89.15 10.71 10.67 11-05111?" 1. 11 45 (0151124): 88. 82 89.22 11. 18 10. 90, n-CoHm 1. 25 53 (0 1E 41), 88. 62 87; 96 11: 38 11.218n-CroHnk. 0.90 65 1a 2a a 88.45 88.74 11.55 11136 n-CuHzt .046 52-C20Haz z 8818- 87.50 11.84 11:84 I 14 3o 1. 36 221130) 87. 92 88 11 12.08 12. 22 n-OwHn 1. 33 4. 6 (Gaming, 87. 73 87. 70 12. 27 12. 18 n-OmHu'L 1.44 32 (0251144 2 87.56 87.47 12.29 12.80 v

Polymerized at 70 with benzoyl peroxide as a catalyst. Precipitated frombenzene with methanol.

b Polystyrenes contained some benzene-insoluble polymer which wasremoved. e Polymerized with ultraviolet light and traces of benzoylperoxide for 96 hrs.; precipitated three times with equal volumes of a:50 ethyl ether/methanol mixture from bend Polymerized with ultravioletlight for 90 hrs., precipitated three times with equal volumes ofmethanol from petroleum ether (B. P. 2838) and benzene.

e Polymerized with ultraviolet light and trace of benzoyl peroxide (144hrs.) precipitated three times with four times the volume of acetonefrom benzene.

f Polymerized with ultraviolet light and trace of benzoyl peroxide (160hrs.) precipe of benzoyl peroxide (160 hrs), preciph Ubbeiohdeviscometer used and specific viscosity determined on polymer solutionsin redistilled anhydrous toluene.

i Not determined refractometrically, softening point in capillary tube.

The polymerization of the C2, C4, Ca, Ca and C10 styrenes was carriedout in the following way. In a standard test tube were placed 2 parts byweight of the monomer and 0.1% by weight of benzoyl peroxide. The air inthe tube was displaced with carbon dioxide and the tube sealed. Thetubes were then heated in a water bath at 70 until no flow could beobserved. The polymers were dissolved in benzene and the filteredsolution added slowly with rapid stirring into a large excess ofmethanol. After 5 such precipitations, the polymers were dried in avacuum dessicator for several days.

The C9, C14, C16 and C18 alkylstyrenes were polymerized in a similarmanner under nitrogen except that only .01 to .03% by Weight of benzoylperoxide was used and the monomers were exposed to ultra-violet light.The approximate temperature under the light was 70 C. Precipitation ofthe benzene solution was carried outwith different solvents (Table IV).

As illustrated the polymers may be prepared in bulk in sealed tubeseither catalyzed by benzoyl peroxide or ultra-violet light or both.Polymers of approximately similar intrinsic viscosities were producedbut this may of course be varied. The polymers were purified by conventional methods (Table IV). The intrinsic viscosities were carried outin toluene in an Ubbelohde viscometer. Transition temperatures (TableIV) were measured by the refractometric method.

The transition temperatures of the polymers have been correlated withthe size of the alkyl group. As shown in Table IV the lowest transitiontemperature is shown by the polymer having n-Cio alkyl groups asside-chains.

With the exception of the polymer from p-n-dodecylstyrene, the intrinsicviscosities reported here are all between 0.90 and 2.00, with themajority having values between 1.0 and 1.6. Polymers of the p-alkylstyrenes having either higher or lower intrinsic viscosities than thoseshown in Table IV may be prepared by suitably varying the conditions ofthe polymerization.

The said p-alkyl-styrenes may be polymerized to high molecular weightsubstances by heating in the presence of catalysts which yield freeradicals or by irradiating with light of a suitable wave-length. Likestyrene itself,

these monomeric p-alkyl styrenes may be polymerized using the varioustechniques commonly employed in the art, that is, by emulsion, bulk,suspension or solution polymerization, with or without the assistance ofpromoters, modifiers, telemerizing agents, etc. Each p-normal alkylstyrene exhibits a tendency to enter into polymerization in a mannerwhich is characteristic of, and common to, all members of the group.Because of this, mixtures of palkyl styrenes may be polymerized to yieldcopolymers which have mixed side-chains, each of the various p-alkylstyrenes present adding readily to the growing polymer chain in thepresence of the others.

The p-alkyl styrenes are valuable in the preparation of polymersincluding homo polymers, heteropolymers, and copolymers of use in theproduction of coatings, adhesives, chewing gum base compositions and thelike. The proportions of such materials will depend on the propertiesdesired in such compositions and the nature and amounts of othercomponents. The polymers of the p-alkyl styrenes may be utilized to giveuniquely desirable characteristicsin such compositions with othercomponents commonly used in such mixtures.

While homopolymers and copolymers of the p-alkyl styrenes have beenmentioned above, the p-alkyl styrenes may be copolymerized with variousother polymerizable materials particularly those containing a CH CHzgroup. As illustrative of such copolymerizing materials there may bementioned, acrylates and methacrylates, styrene and its derivatives,butadiene, chloroprene, vinyl chloride, methyl vinyl ketone, vinylesters such as the acetate, etc. The proportions used in making thecopolymers may vary widely depending on the properties desired. Forexample mole ratios of p-alkyl styrene to co-monomer of from about 1:10to 10:1 may be used. The methods employed may be analogous to those usedabove for the production of polymers of the alkyl styrenes.

Having thus set forth my invention, I claim:

1. p-Alkyl styrenes wherein the alkyl group is a primary normal alkylgroup of at least ten carbon atoms, the p-alkyl styrenes with an alkylgroup up to n-C12H2s having a density ((14 of less than 0.9000, and thep-alkyl styrenes with more than twelve carbon atoms having a meltingpoint above about 26 C.

2. Polymers of p-alkyl styrenes, the alkyl group being a primary normalalkyl group of at least ten carbon atoms.

3. Polymers as set forth in claim 2 in which the alkyl group has fromten to twelve carbon atoms.

4. Polymers as set forth in claim 2 in whichv the alkyl group has morethan twelve but not more than eighteen carbon atoms.

p-alkyl styrenes with an alkyl group up to n-CrzI-Izs having a density(414 of less than 0.9000, and the p-alkyl styrenes with more than twelvecarbon atoms having" a the p-alkyl styrene has a density (r12 of lessthan about 0.9000.

7. Polymers of the styrenes of claim 6. 8. Polymers of mixtures of thestyrenes of claim .6.

9. p-Alkyl styrenes as set forth in claim 5 in which the alkyl group hasmore than twelve carbon atoms and the p-alkyl styrene has a meltingpoint above about 26 C.

10. Polymers of the p-alkyl styrenes of claim 9.

11. Polymers of mixtures of the p-alkyl styrenes of claim 9.

12. Polymers of the p-alkyl styrenes of claim 5.

13. Polymers of mixtures of the p-alkyl styrenes of y m 5. p-Alkylstyrenes wherein the alkyl group is a pri-- 10 mary normal alkyl groupof at least ten carbon atoms, the W ReEeren ees'Cited in the file'ofthis patent FOREIGN PATENTS Switzerland Sept. 30, 1941 OTHER REFERENCESSulzbacher et al.: Jour. Organic .Chem., v0l. 13, pages 303308 (1948; 6pages). j

,Overberger et al.: J. Am. Chem. Soc., 75, 3326-3360,

I 1 20 Juy 953

1. P-ALKYL STYRENES WHEREIN THE ALKYL GROUP IS A PRIMARY NORMAL ALKYLGROUP OF AT LEAST TEN CARBON ATOMS, THE P-ALKYL STYRENES WITH AN ALKYLGROUP UP TO N-C12H25 HAVING A DENSITY (D425) OF LESS THAN 0.9000, ANDTHE P-ALKYL STYRENES WITH MORE THAN TWELVE CARBON ATOMS HAVING A MELTINGPOINT ABOVE ABOUT 26*C.
 2. POLYMERS OF P-ALKYL STYRENES, THE ALKYL GROUPBEING A PRIMARY NORMAL ALKYLK GROUP OF AT LEAST TEN CARBON ATOMS.